Method of sealing an ultracapacitor substantially free of water

ABSTRACT

A method of sealing an ultracapacitor substantially free of water is disclosed. The method includes providing a multilayer cell comprising two solid, non porous current collectors, separated by two porous electrodes with a separator between the two electrodes, sealing the cell with a reclosable hermetic closure. Water inside the closure is dissociated by an applied voltage to the cell and escapes in the form of hydrogen and oxygen when the closure is unmated, the closure is then mated to hermetically seal the cell which is substantially free of water.

This application is a division of application Ser. No. 09/162,532, filedSep. 29, 1998, now U.S. Pat. No. 6,212,061 which is hereby incorporatedby reference in its entirety.

This invention was made with government support under Contract No.38-83CH10093 awarded by DOE. The government may have certain rights inthe invention.

BACKGROUND OF THE INVENTION

Capacitors are storage devices that store electrical energy on anelectrode surface. Electrochemical cells create an electrical charge atelectrodes by chemical reaction. The ability to store or createelectrical charge is a function of electrode surface area in bothapplications. Ultracapacitors, sometimes referred to as double layercapacitors, are a third type of storage device. An ultracapacitorcreates and stores energy by microscopic charge separation at anelectrical chemical interface between electrode and electrolyte.

Ultracapacitors are able to store more energy per weight thantraditional capacitors and they typically deliver the energy at a higherpower rating than many rechargeable batteries. Ultracapacitors comprisetwo porous electrodes that are isolated from electrical contact by aporous separator. The separator and the electrodes are impregnated withan electrolytic solution, which allows ionic current to flow between theelectrodes while preventing electronic current from discharging thecell. Each electrode is in intimate contact with a current collector.One purpose of the current collector is to reduce ohmic loss. If thecurrent collectors are nonporous, they can also be used as part of thecapacitor case and seal.

When electric potential is applied to an ultracapacitor cell, ioniccurrent flows due to the attraction of anions to the positive electrodeand cations to the negative electrode. Upon reaching the electrodesurface, the ionic charge accumulates to create a layer at the solidliquid interface region. This is accomplished by absorption of thecharge species themselves and by realignment of dipoles of the solventmolecule. The absorbed charge is held in this region by opposite chargesin the solid electrode to generate an electrode potential. Thispotential increases in a generally linear fashion with the quantity ofcharge species or ions stored on the electrode surfaces. Duringdischarge, the electrode potential or voltage that exists across theultracapacitor electrodes causes ionic current to flow as anions aredischarged from the surface of the positive electrode and cations aredischarged from the surface of the negative electrode while anelectronic current flows through an external circuit between electrodecurrent collectors.

In summary, the ultracapacitor stores energy by separation of positiveand negative charges at the interface between electrode and electrolyte.An electrical double layer at this location consists of sorbed ions onthe electrode as well as solvated ions. Proximity between the electrodesand solvated ions is limited by a separation sheath to create positiveand negative charges separated by a distance which produces a truecapacitance in the electrical sense.

During use, an ultracapacitor cell is discharged by connecting theelectrical connectors to an electrical device such as a portable radio,an electric motor, light emitting diode or other electrical device. Theultracapacitor is not a primary cell but can be recharged. The processof charging and discharging may be repeated over and over. For example,after discharging an ultracapacitor by powering an electrical device,the ultracapacitor can be recharged by supplying potential to theconnectors.

The physical processes involved in energy storage in an ultracapacitorare distinctly different from the electrochemical oxidation/reductionprocesses responsible for charge storage in batteries. Further unlikeparallel plate capacitors, ultracapacitors store charge at an atomiclevel between electrode and electrolyte. The double layer charge storagemechanism of an ultracapacitor is highly efficient and can produce highspecific capacitance, up to several hundred Farads per cubic centimeter.

Nonaqueous ultracapacitors use an organic salt solution as anelectrolyte. Low levels of moisture and loss of electrolyte bothcontribute to degradation of the ultracapacitor cells. Such degradationadversely affects both performance and life of an ultracapacitor. Hence,proper sealing of an ultracapacitor cell is paramount to the manufactureof a high performance, long-lived cell. Proper sealing has beendifficult because of the aggressive chemical nature of many of theaprotic polar solvents used as cell electrolyte solvents. Many of thecommon adhesives such as epoxies, cyanate esters, silicones and ethylenevinyl acetates fail mechanically, lose adhesion or permit defusion ofsolvent through sealant. The common failure of sealants requires that asecondary container be used to completely contain and seal theultracapacitor cell. The present invention provides a hermetic and leakproof seal through a primary seal with the current collectors of theultracapacitor thus eliminating the need for a secondary container.Further, the present invention uses a resealable closure mechanism thatallows repair of the cell and removal of internal moisture by release ofgas pressure.

SUMMARY OF THE INVENTION

The invention relates to an ultracapacitor that comprises at least onecell comprising two solid, nonporous current collectors, two porouselectrodes separating the current collectors, a porous separator betweenthe electrodes and an electrolyte occupying pores in the electrodes andseparator. The cell is sealed with a reclosable hermetic closure.

The invention also relates to a stack of ultracapacitor cells comprisinga plurality of bipolar double layer ultracapacitor cells in stackedrelationship, at least one cell comprising porous, oppositely chargedelectrodes with an ionically charged separator disposed between theelectrodes. The stack includes a non-porous current collector betweeneach cell with each current collector having adjoining polarizedelectrodes of different cells bonded thereto. An electrolyte saturatesthe electrodes and separators. At least one cell of the stack is sealedwith a reclosable hermetic closure.

In another aspect, the invention relates to a method of making anultracapacitor, comprising providing a multilayer cell comprising twosolid, nonporous current collectors, two porous electrodes separatingthe current collectors, a porous separator between the electrodes and anelectrolyte occupying pores in the electrodes and separator. The cell isthen sealed with a reclosable hermetic closure.

In a final aspect, the invention relates a method of making a stack ofultracapacitor cells. In the method, a plurality of bipolar double layerultracapacitor cells are provided in stacked relationship. At least onecell comprises porous, oppositely charged electrodes with an ionicallycharged separator disposed between the electrodes. a non-porous currentcollector is provided between each cell with each current collectorhaving adjoining polarized electrodes of different cells bonded thereto.The electrodes and separators are saturated with electrolyte and atleast one cell of the stack is sealed with a reclosable hermeticclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a front sectional view of an ultracapacitor;

FIG. 2 is a front sectional view of a series stack of ultracapacitorcels;

FIG. 3 is a schematic representation of an ultracapacitor cell sealedwith a reclosable hermetic closure; and

FIG. 4A is a sectional views of an unclosed reclosable hermetic closureand

FIG. 4B is a sectional view of a closed reclosable hermetic closure.

DETAILED DESCRIPTION OF THE INVENTION

The sealing method of the invention may be used to make a wide varietyof ultracapacitors such as described in U.S. Pat. Nos. 5,464,453;5,420,747; 5,150,283; 5,136,472; and 4,803,597; as well as PCTApplication WO96/11486 (PCT/US95/12772; Apr. 18, 1996), all of which areincorporated herein by reference. FIGS. 1 and 2 herein, are based on PCTApplication WO 96/11486 and show non-limiting examples of structuresthat can be sealed according to the present invention.

In all of the Figures of this application, like structures areidentified by the same numbers.

Referring to FIG. 1, ultracapacitor 10 includes a nonconductiveenclosing body 12, a pair of carbon electrodes 14 and 16, an electronicporous separator layer 18, an electrolyte 20, a pair of conductivelayers which are current collectors 22 and 24 and electrical leads 26and 28, extending from the current collectors 22 and 24. One of the pairof current collectors 22 and 24 is attached to the back of eachelectrode 14 and 16. In FIG. 1, electrodes 14 and 16 can each representa plurality of electrodes so long as the electrodes are porous toelectrolyte flow.

The current collectors 22, 24 can be made of a metal foil such asaluminum, conductive polymer or polymer with a conductive filler.Carbon-filled polyethylene is a preferred material for the currentcollectors 22,24 of the present invention.

The electronic separator 18 is preferably made from a highly porousmaterial which acts as an electronic insulator between the carbonelectrodes 14 and 16. The separator 18 assures that opposing electrodes14 and 16 are never in contact with one another. Contact betweenelectrodes can result in a short circuit and rapid depletion of thecharges stored in the electrodes. The porous nature of the separator 18allows movement of ions in the electrolyte 20. A wide variety of typesand arrangements of separation layers can be employed, as those ofordinary skill in the electrochemical arts realize. Separation layersare usually made from nonconductive materials such as cellulosicmaterials; glass fiber; polymers such as polyesters or polyolefins; andthe like. In those embodiments in which the separator layers will be incontact with sealant material, they should have a porosity sufficient topermit the passage of sealant and should be resistant to the chemicalcomponents in the sealant. In a typical ultracapacitor, the separatorlayers have a thickness in the range of about 0.5 mil to about 10 mils.Preferred separators 18 are porous polypropylene and tissue cellulosicmaterials. Exemplary organic solvents for electrolyte 20 include but arenot limited to nitriles such as acetonitrile, acrylonitrile andpropionitrile; sulfoxides such as dimethyl, diethyl, ethyl methyl andbenzylmethyl sulfoxide; amides such as dimethyl formamide andpyrrolidones such as N-methylpyrrolidone. Preferably, the electrolyte 20includes a polar aprotic organic solvent such as a cyclic ester, chaincarbonate, cyclic carbonate, chain ether and/or cyclic ether solvent anda salt. Preferred cyclic esters are esters having 3 to 8 carbon atoms.Examples of the cyclic esters include β-butyrolactone, γ-butyrolactone,γ-valerolactone and δ-valerolactone. The chain carbonates are preferredto be carbonates having 3 to 8 carbon atoms. Examples of the chaincarbonates include dimethyl carbonate, diethyl carbonate, dipropylcarbonate, methyl ethyl carbonate, methyl propyl carbonate and ethylpropyl carbonate. The preferred cyclic carbonates have 5 to 8 carbonatoms. Examples of the cyclic carbonates include 1,2-butylene carbonate,2,3-butylene carbonate, 1,2-pentene carbonate, 2,3-pentene carbonate andpropylene carbonate. The preferred chain ethers have 4 to 8 carbonatoms. Examples of the chain ethers include dimethoxyethane,diethoxyethane, methoxyethoxyethane, dibutoxyethane, dimethoxypropane,diethoxypropane and methoxyethoxypropnane. The preferred cyclic ethershave 3 to 8 carbon atoms. Examples of the cyclic ethers includetetrahydofuran, 2-methyl-tetrahydrofuran, 1,3-dioxolan, 1,2-dioxolan,2-methyldioxolan and 4-methyl-dioxolan.

Suitable electrolyte salts include quaternary ammonium salts such astetraethylammonium tetraflouroborate ((Et)₄NBF₄), hexasubstitutedguanidinium salts such as disclosed in U.S. Pat. No. 5,726,856, thedisclosure of which is incorporated herein by reference, and lithiumsalts such as disclosed by Ue et al., Mobility and Ionic Association ofLithium Salts in a Propylene Carbonate-Ethyl Carbonate Mixed Solvent,Electrochem. Soc., vol. 142, No. Aug. 8, 1995, the disclosure of whichis incorporated herein by reference.

In a preferred embodiment, the electrodes 14, 16 in FIG. 1, are bothcarbon electrodes on carbon-filled polyethylene current collectors. Theelectrode can be fabricated by a forming process or by pressingelectrode materials in a die and slurry pasting or screen printingcarbon as a paste with a liquid phase binder/fluidizer. The liquid phasemay be water or an electrolyte solvent with or without a thinner such asacetone. Both dry and wet electrode formations may include a binder suchas polymers, starches, Teflon® particles or Teflon® dispersions inwater.

The enclosing body 12 can be any known enclosure means commonly usedwith ultracapacitors. It is an advantage to minimize the weight of thepackaging means to maximize the energy density of the ultracapacitor.Packaged ultracapacitors are typically expected to weigh 1.25 to 2 timesmore than the unpackaged ultracapacitor. The electrical leads 26 and 28extend from the current collectors 22 and 24 through the enclosing body12 and are adapted for connection with an electrical circuit (notshown).

Individual ultracapacitor cells can be stacked in series to increaseoperating voltage. The optimum design is to have adjacent cellsseparated with only a single current collector. This collector isnonporous so that no electrolytic solution is shared between cells. Thistype of design is called bipolar and is illustrated in FIG. 2 of thedrawings. In a bipolar double layer capacitor, one side of the currentcollector contacts a positive electrode and the other side contacts anegative electrode of an adjacent cell. A series stack 40 of the highperformance bipolar double layer cells 30 (A, B, C and D) is illustratedin FIG. 2. In FIG. 2, each pair of polarized carbon electrodes, 14, 16is separated with a separator 18. A current collector 32 is attached atone surface to charged electrode 14 of a first cell. Attached to anopposite surface of the current collector 32, is an oppositely chargedelectrode 16 of a second cell. If one side of the current collector 32is in contact with the negative electrode for a first capacitor cell“A,” then the other side of the same current collector 32 is in contactwith a positive electrode for an adjacent cell “B.” A sufficient amountof an electrolyte 20 is introduced such that the electrolyte 20saturates the electrodes 14 and 16 and separator 18 within each cell.Exterior current collectors 22 and 24 are placed at each end of thestack.

The internal current collectors 32 of the series stack of cells arepreferably carbon filled polyethylene layers designed to separate theelectrolyte 20 between adjacent cells. The exterior current collectorsare also nonporous such that they can be used as part of the externalcapacitor case seal, if necessary. The electronic separator 18 islocated between the opposing carbon electrodes 14 and 16 within aparticular capacitor cell. The electronic separator 18 allows ionicconduction via charged ions in the electrolyte.

In the present invention, the ultracapacitor cell of FIG. 1 and at leastone cell of the stack of FIG. 2 are sealed with a reclosable hermeticclosure. FIG. 3 is a schematic representation of an ultracapacitor cellsealed with a reclosable hermetic closure according to the presentinvention and FIGS. 4A and 4B are sectional views of a preferredembodiment of a reclosable hermetic closures according to the inventionboth unclosed (FIG. 4A) and closed (FIG. 4B).

In FIG. 3, cell 10 includes current collectors 22, 24 which preferablyare made of a material that is compatible with the material of thereclosable hermetic closure as hereinafter described. Preferably, thecollectors 22, 24 are carbon filled polyethylene. The cell 10 includes aseparator 18 and electrodes 14, 16. The cell 10 is sealed on at leastone side by a reclosable hermetic closure represented schematically at120. The remaining sides are sealed with sealant 132. The closure 120includes interlocking closure elements 122, 124 and supportingpolyolefinic film portions 128 which can be polyethylene orpolypropylene film or the like, and which are attached to respectivecurrent collectors 22, 24 by means of heat weld joints 130. The closure120 can be any type that can be reopened to release gas and reduceinternal pressure of the cell 10 and reclosed to form an hermetic seal.Suitable closures 120 include mechanical closures and adhesive closuresand the like. Preferably, closure 120 is a mechanical closure formed byinterlocking elements such as interlocking channel elements,interlocking rib and groove profiles such as zipper closures andinterlocking male and female elements as hereinafter described withreference to FIGS. 4A and 4B. The types of closures used with Ziploc®(DowBrands, Indianapolis, Ind.) bags are preferred closures 120.

FIGS. 4A and 4B show a preferred closure 120 which is an interlockingmale element and female element type. Referring to FIGS. 4A and 4B,closure 120 comprises oppositely disposed male and female closureelements 122 and 124 and ribs 126 for guiding the elements 122 and 124into interlocking engagement when a deforming compressive force isapplied to the outer surfaces of film portion 128. The male closureelement 122 consists of a single blunt-shaped profile member whichextends from film portion 128 and has a blunt head extremity 136, whichis suited for interlocking with the cavity 138 formed by profile members140 of the female element 124.

The means employed by the embodiment of FIGS. 4A and 4B for guiding theextremity 136 and cavity 138 into interlocking engagement comprisesflexible ribs 126 which flank the profile member 132 on both sides andwhich are positioned generally adjacent the profile member 132. Each rib126 is characterized by a bevel 144 that slopes downwardly towardsprofile member 132. During closure, the bevels 144 contact and guiderespective extremities 138 of the female element 124 into aninterlocking engagement with blunt head extremity 136 as shown in FIG.4B.

The closure 120 has a differential pressure requirement that relates toan internal release pressure of the cell. Preferably the releasepressure (the pressure which will cause release of the closure 120) is afactor of about 10 to about 20 times greater than internal cellpressure. Blunt head extremity 136 has an angled profile. Hence, whenthe blunt head extremity 136 is in interlocking relationship with cavity138 as shown in FIG. 4B, one side is tightly urged against one wall ofthe cavity 138 to provide a seal that is released only upon applicationof the release pressure specified by the present invention.

The ultracapacitor cell of the present invention is sealed by thereclosable hermetic closure at one or more sides and is otherwise sealedby the application of pressure and/or heat with or without a sealant atremaining sides. Many different types of sealants can be used in thepresent invention and the term is meant to encompass, “glues”, or“pastes.” Sealants are described, for example, in the Kirk-OthmerEncyclopedia of Chemical Technology, 3rd Edition, Vol. 1, pp.488-508(1978), and in The Condensed Chemical Dictionary, 10th Edition, 1981,Van Nostrand Reinhold Company. In general, the selected sealant shouldbe chemically resistant to electrolyte. It should also be capable ofwithstanding operating temperatures of the ultracapacitor withoutsubstantial degradation. Moreover in those embodiments where the sealantcontacts the separators, it should be capable of flowing through thethickness of the separator layers. Once cured, the sealant should besubstantially impermeable to the flow or passage of electrolyte.

Heat-curable sealants may be used in some embodiments. Moisture-curedsealants or externally-cured materials may be used. Other embodimentsmay use air-curable or pressure-sensitive sealants, such as “hot melt”glues. Illustrative sealants include those based on acrylic, ethylenesuch as ethylene vinyl acetate (EVA) copolymer, silicone, rubber, epoxymaterials, or combinations of these materials. Commercial examplesinclude the materials commonly referred to as “hot glues.”

The sealants are usually in the form of liquids, pastes, or solids. Asealant may be applied to one or both of the facing surfaces of theseparators or other surfaces. Many techniques are available for applyingsealant. Known application techniques include the use of a spatula,brush, roller, spray, or glue gun. As one example, a bead, strip or“ring” of sealant is applied along the peripheral area 68 of one of theseparator layers. Alternatively, individual droplets of sealant can bedeposited at sites in the peripheral area 68 with the droplets flowingand covering the peripheral area 68 upon the application of pressure,vacuum and/or heat. As yet another alternative, at least one of theseparator layers 18 can be pre-impregnated with sealant. All of thesetechniques cause the sealant to form a continuous layer. In general, theparticular method of deposition is not critical, as long as the sealantis applied to locations where it will eventually form a seal afterpressure or vacuum is released. The ultracapacitor becomes sealed by abarrier which is perpendicular to the horizontal capacitor layers whichare encased in the barrier.

A compressive force can be applied to promote the flow of thesealant—especially in the case of sealant compositions with very highsoftening points or glass transition temperatures, such as the EVA basedtypes. Compression can be applied indirectly to the sealant throughupper ultracapacitor layers by means of a mechanical press.

The following example is illustrative of the invention.

EXAMPLE

A film portion with a male closure element as shown in FIGS. 4A and 4Bwas heat welded to one side of a carbon filled polyethylene currentcollector. The current collector was then screen printed with acarbon-electrolyte slurry to form an electrode. Another currentcollector with a female element was similarly prepared. A porouspolyethylene separator was placed between the two current collectorswith carbon electrodes and the package was heat welded on the threesides that did not have the attached closure. Edges of the separatorwere sealed with HYSOL 7811, a polyamide sealant from Hysol Engineering& Industrial Productons Division of Dexter Corporation, to preventwicking of electrolyte. An electric potential between 1 and 2 volts wasapplied to the cell so that moisture trapped within the cell washydrolyzed, resulting in the formation of gaseous products. The closurewas then opened to allow the gases to escape and then immediatelyreclosed to provide a hermetically sealed cell.

What is claimed:
 1. A method of making an ultracapacitor, comprising;(A) providing a multilayer cell comprising two solid, nonporous currentcollectors, two porous electrodes separating said current collectors, aporous separator between said electrodes and an electrolyte occupyingpores in said electrodes and separator; and (B) sealing said cell with areclosable hermetic closure, wherein said sealing comprises applying anelectric potential to said cell to disassociate water within said cellto hydrogen and oxygen; unmating said reclosable hermetic closure topermit the escape of said hydrogen and oxygen; and mating saidreclosable hermetic closure to seal said cell substantially free ofwater.
 2. The method of claim 1, wherein (B) further comprises (i)attaching a first half of said reclosable hermetic closure to a first ofsaid current collectors and coating said first current collector withone of said porous electrodes, (ii) attaching a second half of saidreclosable hermetic closure to a second of said current collectors andcoating said second current collector with one of said porouselectrodes, (iii) placing said separator between said coated first andsecond current collectors and (iv) mating said halves of said reclosablehermetic closure to seal said cell.
 3. The method of claim 1, furthercomprising heat sealing at least one side of said cell.
 4. A method ofmaking a stack of ultracapacitor cells, comprising: (A) providing instacked relationship, a plurality of bipolar double layer ultracapacitorcells, at least one comprising porous, oppositely charged electrodeswith ionically charged separator disposed between said electrodes; (B)providing a non-porous current collector between each cell with eachcurrent collector heaving adjoining polarized electrodes of differentcells bonded thereto; (C) saturating said electrodes and separators withelectrolyte; and (D) sealing at least one of said cells with areclosable hermetic closure, wherein said sealing comprises applying anelectric potential to said cell to disassociate water within said cellto hydrogen and oxygen; unmating said reclosable hermetic closure topermit the escape of said hydrogen and oxygen; and mating saidreclosable hermetic closure to seal said cell substantially free ofwater.
 5. The method of claim 4, wherein (D) further comprises (i)attaching a first half of said reclosable hermetic closure to a first ofsaid current collectors and coating said first current collector withone of said porous electrodes, (ii) attaching a second half of saidreclosable hermetic closure to a second of said current collectors andcoating said second current collector with one of said porouselectrodes, (iii) placing said separator between said coated first andsecond current collectors and (iv) mating said halves of said reclosablehermetic closure to seal said cell.